Separation of Co (II) and Ni (II) from Sulphate-Chloride Leach Liquor Using PC88A 29

Separation of Co(II) and Ni(II) from Sulphate-Chloride

Leach Liquor Using PC88A
P.K. Parhi, E. Padhan, A. Palai, K.C. Nathsarma and K. Sarangi
Regional Research Laboratory (CSIR)
Bhubaneswar-751013

ABSTRACT: Solvent extraction studies for separation of cobalt and nickel was carried out using PC88A after
separation of iron(III), copper and zinc from a typical leach liquor of secondaries bearing 11.8 kg/m3 iron(III),
24.8 kg/m3 copper, 0.23 kg/m3 zinc, 3.8 kg/m3 cobalt, 35.2 kg/m3 nickel, 176.3 kg/m3 chloride and 48.9 kg/m3
sulphate. After separation of iron(III), copper and zinc, the solution contained only cobalt and nickel in the
chloride-sulphate solution. At the copper extracion stage the leach liquor was diluted twice for which the
composition of the leach liquor became 1.9 kg/m3 cobalt, 17.6 kg/m3 nickel, 88 kg/m3 chloride and 24.45 kg/m3
sulphate. Extraction of cobalt was carried out with 0.09M PC88A. The effect of pH and [PC88A] on cobalt
extraction was studied. The McCabe-Thiele plot for extraction of cobalt was constructed at pH 3.05 using 0.09 M
PC88A to read 2-stages at 1 : 1 phase ratio. Extraction of nickel was carried out with 0.6 M neutral PC88A within
the feed solution pH range 0.95–6.7. The McCabe-Thiele plot for extraction of nickel was constructed using 0.6
M PC88A and the isotherm read 2-stages at O : A ratio of 5 : 4. The stripping studies for cobalt loaded organic
and nickel loaded organic were carried out with H2SO4.

1. INTRODUCTION liquor containing 1.9 kg/m3 cobalt, 17.6 kg/m3

A typical leach liquor of secondaries bearing 11.8
kg/m3 iron(III), 24.8 kg/m3 copper, 0.23 kg/m3
zinc, 3.8 kg/m3 cobalt, 35.2 kg/m3 nickel, 176.3
kg/m3 chloride and 48.9 kg/m3 sulphate obtained
from Korea Institute of Geoscience and Mineral
Resources (KIGAM) was processed at
Regional Research Laboratory (CSIR),
Bhubaneswar for separation of metal ions using
solvent extraction. After separation of iron(III),
zinc and copper (Sarangi et al., Press), the leach
liquor contained cobalt and nickel in the chloride
and sulphate solution. After extraction of Fe(III),
the leach liquor was diluted twice prior to
copper(II) extraction for which the composition
of the leach liquor was 1.9 kg/m3 cobalt, 17.6
kg/m3 nickel, 88 kg/m3 chloride and 24.45 kg/m3
sulphate. A lot of work on separation of cobalt
and nickel (Reddy et. al., 1999, Thakur et al.,
1998, Tsakiridis et al., 2004) from aqueous
solutions has been carried out earlier.
2. EXPERIMENTAL
The commercial extractants PC88A in distilled
kerosene (b.p. 160-220°C) was used as the extrac-
tant for separation of cobalt and nickel. The leach
nickel, 88 kg/m3 chloride and 24.45 kg/m3
sulphate was used in the study. Desired volumes
of the leach liquor and extractant diluted in
kerosene were equilibrated manually in a
separating funnel for 5 minutes and after phase
disengagement, the aqueous phase was separated
followed by the measurement of its equilibrium
pH and determination of its metal content in the
raffinate by AAS. The concentrations of metal
ions in the organic phase were calculated from
the difference between the concentration in the
aqueous phase before and after extraction.
3. RESULTS AND DISCUSSION
3.1 Extraction of Cobalt
Extraction of cobalt from the Co-Ni solution was
carried out with neutral 0.09 M PC88A at 1 : 1
phase ratio. To study the effect of pH on
extraction of cobalt, the pH of the Co-Ni solution
was adjusted in the range 1.0 to 6.25 by adding
NaOH/H2SO4 solutions. The equilibrium pH was
varied within 1.4 to 6.3. Extraction of cobalt
increased from 0.65 to 91.76% with increasing
equilibrium pH from 1.4 to 6.3 (Fig. 1). At
equilibrium pH 3.05, the percentage of cobalt
30  Mineral Processing Technology (MPT 2007)
extraction was 91.5 with co-extraction of 4.84% solution (pH 3.05) and 0.09 M PC88A at O:A
nickel. ratios within 1 : 5 to 5 : 1, while keeping the total
volume of phases at 48 cm3. The extraction
100 isotherm read 2-stages at 1 : 1 phase ratio. The
Percentage extraction

counter-current simulation study for extraction of

80
Co
60
Ni
40
20
0 was carried out with various concentrations of
1 3
Equilibrium pH
Fig. 1: Effect of equilibrium pH on extraction of
Co and Ni
To study the effect of [PC88A] on extraction of
cobalt, the concentration of PC88A was varied
from 0.02 to 0.25 M and the pH of aqueous
solution was kept at 2.15. The aqueous and the
organic phases were contacted for five minutes at
1 : 1 phase ratio and after phase disengagement,
the raffinate was separated and its equilibrium
pH was measured. The experimental data showed
increase in percentage extraction from 10.39 to
91.5 for cobalt with co-extraction of 0.88 to
31.58% nickel (Fig. 2).
100
Percentage extraction
cobalt in the above conditions showed
quantitative extraction (99.38%) of cobalt. For
stripping studies, sufficient amount of cobalt
loaded organic was generated using 0.09 M
PC88A at pH 3.05 and 1 : 1 phase ratio.
The stripping study for cobalt loaded PC88A
H2SO4 (0.05 to 0.5%) at equal phase ratio. The
5 7 percentage stripping increased from 11.59 to 100
with increase in H2SO4 concentration. Finally,
0.5% H2SO4 was chosen to strip the cobalt loaded
organic. The cobalt-stripping isotherm was
constructed with 0.5% H2SO4 at O : A ratios
within 1 : 5 to 5 : 1 while keeping the total
volume of phases at 48 cm3. The isotherm read 2-
stages at A : O ratio of 1 : 2. Accordingly, the
counter-current simulation study carried out at
the above conditions for cobalt stripping
confirmed the theoretical prediction.
3
2.5
2

3
[Co]Org., kg/m

80 1.5
Co
60 Ni
1
40
0.5
20

0 0
0 0.1 0.2 0.3 0 1 2 3
3
[PC88A], M [Co]Aq., kg/m
Fig. 2: Effect of [PC88A] on extraction of Co and Fig. 3: Extraction isotherm for Co using 0.09 M
Ni NaPC88A

The McCabe-Thiele plot (Fig. 3) for extrac-

tion of cobalt was constructed with the feed
Separation of Co (II) and Ni (II) from Sulphate-Chloride Leach Liquor Using PC88A
3.2 Extraction of Nickel
Extraction of nickel from the cobalt-barren
raffinate was carried out using neutral PC88A in
kerosene. The effect of pH on extraction of
nickel was studied with 0.6 M NaPC88A within
the feed solution pH range 0.95-6.7 (equilibrium
pH range 6.00-7.25) at 1 : 1 phase ratio. The
percentage nickel extraction increased from
77.31 to 92.69 with increase in pH from 0.95 to
2.6 but with further increase of pH, the
percentage extraction remained constant at 92.69
(Fig. 4).
31
The McCabe-Thiele plot (Fig. 6) for extraction of
nickel was constructed using 0.6 M PC88A at O :
A ratios within 1 : 5 to 5 : 1 while keeping the
total volume of phases 48 cm3. The isotherm read
2-stages at O : A ratio of 5 : 4. The counter-
current simulation study for extraction of nickel
at the predicted conditions was carried out to
generate requisite volume of loaded organic for
further studies.
20

95 15

[Ni]org, kg/m
3
Percentage Ni extraction

90 10

85 5

80 0
0 5 10 315 20
75 [Ni]Aq. kg/m
5.5 6.5 7.5 Fig 6: Extraction isotherm of Ni using 0.6 M
Euilibrium pH PC88A

Fig. 4: Effect of euilibrium pH on extraction of Ni Stripping of nickel loaded organic was

The effect of [PC88A] on extraction of nickel
was studied within the range of 0.2 to 1.0 M. The
initial pH of aqueous solution was kept at 5.85.
The experimental data shown in Fig. 5 indicate
increase in percentage extraction from 20.52 to
99.46 with increase of [PC88A] from 0.2 M to
1.0 M.
100
Percentage Ni
carried out with H2SO4 concentrations within 0.5-
8.0% by equilibrating the phases at 1 : 1 phase
ratio; the percentage nickel stripping increased
from 2.27 to 100% with increase in acid
concentration. The McCabe-Thiele plot for
stripping of nickel constructed with 8.0% H2SO4
at O : A ratios within 1 : 5 to 5 : 1, while keeping
the total volume of phases 48 cm3, showed
quantitative stripping of the Ni-LO in 2-stages at
O : A phase ratio of 4 : 1. Accordingly, a counter-
current stripping study was carried out to confirm

80 the predicted data.

extraction

60
40
20 CONCLUSION
0
Extraction and separation of cobalt and nickel
0 0.5 1 1.5 from the 1.9 kg/m3 cobalt, 17.6 kg/m3 nickel, 88
[PC88A], M kg/m3 chloride and 24.45 kg/m3 sulphate solution
Fig. 5: Effect of [PC88A] on extraction of Ni
have been carried out using 0.09 and 0.6 M
PC88A, respectively. Extraction of cobalt and
nickel increased with increasing equilibrium pH.
32  Mineral Processing Technology (MPT 2007)
Extraction of cobalt was carried out from a 3.05
pH solution in 2-stages at equal phase ratio and
stripping of the Co-LO was carried out with 0.5%
H2SO4. Extraction of nickel from the Co-free
solution was carried out in 2-stages at O : A = 5 :
4 using 0.6 M PC88A. The Ni-LO was stripped
with 8% H2SO4 in 2-stages at O : A = 4 : 1.
REFERENCES
[1] Reddy, B.R., Parija, C. and Bhaskara Sarma,
P.V.R., Processing of solutions containing nickel
and ammonium sulphate through solvent
extraction using PC-88A, Hydrometallurgy, 53,
11-17 (1999).
[2] Sarangi, K., Parhi, P.K., Padhan, E., Palai, A.K.,
Nathsarma, K.C. and Park, K.H. Separation of
iron(III), copper(II) and zinc(II) from a
mixedsulphate/chloride solution using TBP, LIX
84I and Cyanex 923, Separation and Purification
Technology, In Press.
[3] Thakur, N.V. and Mishra, S.L., Separation of Co,
Ni and Cu by solvent extraction using di-(2-
ethylhexyl) phosphoric acid, PC88A,
Hydrometallurgy, 48, 277-289 (1998).
[4] Tsakiridis, P.E. and Agatzini, S.I., Simultaneous
solvent extraction of cobalt and nickel in the
presence of manganese and magnesium from
sulfate solutions by Cyanex 301,
Hydrometallurgy, 269-278 (2004).